CN106883872A - Deep desulfurization device and method for gasoline - Google Patents
Deep desulfurization device and method for gasoline Download PDFInfo
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- CN106883872A CN106883872A CN201510931413.6A CN201510931413A CN106883872A CN 106883872 A CN106883872 A CN 106883872A CN 201510931413 A CN201510931413 A CN 201510931413A CN 106883872 A CN106883872 A CN 106883872A
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- gasoline
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- petrol
- desulfurization
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 67
- 230000023556 desulfurization Effects 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 43
- 239000011593 sulfur Substances 0.000 claims abstract description 43
- 238000006266 etherification reaction Methods 0.000 claims abstract description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001993 dienes Chemical class 0.000 claims abstract description 10
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005520 cutting process Methods 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 238000012546 transfer Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 230000003197 catalytic effect Effects 0.000 claims description 30
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 28
- 238000004821 distillation Methods 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 230000008859 change Effects 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 235000009508 confectionery Nutrition 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000005804 alkylation reaction Methods 0.000 abstract description 7
- 230000029936 alkylation Effects 0.000 abstract description 6
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 description 26
- 238000005516 engineering process Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 13
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000006276 transfer reaction Methods 0.000 description 10
- -1 alkyl sulfur Chemical compound 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229930192474 thiophene Natural products 0.000 description 6
- 238000004148 unit process Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A gasoline deep desulfurization device comprises a prehydrogenation gasoline cutting tower, a light gasoline etherification reactor, a catalytic reaction rectifying tower and a heavy gasoline hydrodesulfurization reactor; the invention also relates to a gasoline deep desulfurization method: (1) after mixing the full-fraction gasoline with hydrogen, firstly entering a pre-hydrogenation light gasoline cutting tower, removing diolefin and mercaptan, and finishing cutting light and heavy components to obtain light gasoline at the top of the tower and heavy gasoline at the bottom of the tower; (2) the light gasoline at the top of the tower enters a light gasoline etherification reactor to carry out etherification reaction with methanol; (3) the heavy gasoline at the bottom of the tower enters a catalytic reaction rectifying tower, a gasoline alkylation sulfur transfer catalyst is filled in the catalytic reaction rectifying tower, and thiophene sulfides in the gasoline are subjected to alkylation reaction with light olefins under the action of the catalyst to obtain middle gasoline after the tower top is desulfurized and heavy gasoline fraction at the bottom of the tower; (4) and the olefin content in the tower bottom heavy gasoline fraction is reduced to 25%, and the heavy gasoline fraction enters the heavy gasoline hydrodesulfurization reactor to obtain the tower bottom desulfurized heavy gasoline.
Description
Technical field
The present invention relates to a kind of deep desulfurization of gasoline group technology containing alkyl sulfur transfer techniques.
Background technology
With the development and the enhancing of environmental consciousness of national economy, countries in the world are all carried out to the sulfur content of gasoline
The developed countries such as considered critical, America and Europe have implemented " sweet gasoline " (gasoline since two thousand nine
Sulfur nutrient is not more than 10 μ g/g) new standard, China from 2010 in the whole country gasoline perform
The standard of state III (gasoline sulfur nutrient is not more than 150 μ g/g), is determined on January 1st, 2014 for " state
Four " (gasoline sulfur nutrient is not more than 50 μ g/g) gasoline standard implements in full the date, " state five " car
Will be in issue, transitional period to 2017 before the end of the year 2013 with gasoline standard (sulfur content is not more than 10ppm)
The end of the year.
China's gasoline is constituted and (accounts for more than the 80% of China's gasoline product) based on FCC gasoline component,
The characteristics of with high-sulfur, alkene high.Hydrogen addition technology is the important means for effectively removing sulphur in FCC gasoline,
It is main based on selective hydrodesulfurization technology at present.Wherein, the Prime-G+ technologies of AXENS companies
Relatively broad commercial Application production Europe V clean gasoline is obtained.But due to the difference of domestic and international oil property
It is different, for treatment China high-sulfur, alkene FCC gasoline high, when ultra-deep hydrodesulfuration is carried out, use
Independent hydrodesulfurization technology can bring alkene to be significantly hydrogenated with saturation, cause loss of octane number larger, economy
It is poor.At present, it is domestic still to lack the production that mature technology is used for state V standard clean gasoline.
US6,692635 describe a kind of low-sulphur oil production technology, are characterized in that full cut catalytic gasoline is former
Material selectively removing alkadienes first in selective hydrogenation reactor (first reactor), olefinic double bonds are different
Structure, mercaptan is converted into higher boiling sulfur compound.Then, selective hydrogenation product is fractionated in a fractionating column
It is light fraction and heavy distillat.Heavy distillat is first in the first reaction zone of hydrogenation reactor (second reactor)
MoO3-CoO/Al2O3It is hydrogenated with catalyst, by unsaturated sulfide (such as thiophene and its alkylated substituted thiazoline
Fen) saturation sulfide (such as thiophane or mercaptan) is converted into, then, in second reaction zone
NiO/Al2O3It is hydrogenated with catalyst, saturation sulfide is converted into H2S.The desulfurization degree of the patented method leads to
Often it is 80.0%~92.0%, product sulfur content is generally 96 μ g/g~240 μ g/g, research octane number (RON)
(RON) 1.4~3.0 units are lost.It has the disadvantage to can not meet oil refining enterprise's production clean gasoline sulphur
The technical need of content ≯ 10 μ g/g.
CN101270301A discloses a kind of Etherification of Light FCC Gasoline technique and the catalytically cracked gasoline containing the technique
Method for modifying, is by the alkadienes and mercaptan sulfur in FCC gasoline selective hydrogenation and removing gasoline, after hydrogenation
By full distillation gasoline cut into gently, weigh two components.Substantial amounts of Tertiary olefin has been concentrated in light petrol, through with first
Alcohol is etherified into ether compound, the hydrogenated desulfurization drop alkene of heavy petrol in the presence of catalyst for etherification through two sections
Hydrocarbon, after removing sulfide and reduction olefin(e) centent, the aromatic hydrocarbons in heavy petrol after hydrogenation is more, can be through taking out
Aromatic hydrocarbons is carried, gasoline component of the heavy petrol rich in alkane after extracting aromatic hydrocarbons can make the raw material of steam cracking ethene,
Also it is clean gasoline product that can be reconciled with etherified benzine.The technology light petrol cut point is 60 DEG C, weight vapour
After oily hydrodesulfurization, sulfur content in 100 μ g/g, can not meet oil refining enterprise's production clean gasoline sulfur content ≯
The technical need of 10 μ g/g.
CN201310256949.3 discloses a kind of method for modifying of catalytic gasoline of whole fraction.Full cut
Catalytically cracked gasoline raw material enters pre- hydroprocessing unit and removes alkadienes.Effluent is de- into selective hydrogenation
It is and pungent into octane value recovering reactor after sulphuring treatment reactor, with Hydrobon catalyst haptoreaction
Alkane value recovers catalyst haptoreaction, and effluent obtains the upgraded products of low sulfur-bearing after gas-liquid separation.The hair
The bright catalytic gasoline of whole fraction by total sulfur content less than 400ppm carries out hydrodesulfurization and octane
Value recovery treatment, below 50ppm is down to by upgraded products sulfur content, while loss of octane number is less than one
Unit.
The A of CN 104650975 disclose a kind of method of deep desulfurization of gasoline；Gasoline stocks initially enter
One reactor removes alkadienes mercaptan heaviness simultaneously, and light, heavy petrol is fractionated into subsequently into fractionating column cutting,
After heavy petrol enters the most sulfide of second reactor removing, product enters back into the 3rd reactor and enters
Traveling one-step desulfurization, the heavy petrol hydrodesulfurization product for obtaining is mixed to get qualified gasoline and produces with light petrol
Product；This method is realizing further deep desulfuration by after second reactor, increasing by the 3rd reactor
Meanwhile, second reactor reaction severity is significantly reduced, realize loss of octane number and hydrogen consumption is optimized.
CN 103184071A disclose a kind of method of gasoline desulfurization：Gasoline comprising a small amount of diesel component evaporates
Divide and hydrogen is mixed into pre-hydrogenator；Pre- hydrogenation products are fractionated into fractionating column, from fractionating column
Tower top light component out enters directly as low-sulphur oil blend component from Fractionator Bottom heavy constituent out
Water scrubber removes basic nitrogen compound, enters back into during the alkene thiophene alkylation reactor of one group of series connection makes heavy petrol
Exposure fen class sulfide weightening, enter catalytic distillation tower from alkylation reactor gasoline component out, urging
Changing in the presence of destilling tower top alkene exposes alkylated phenothiazine catalyst makes remaining exposure fen class sulfide increase weight, together
When by gasoline be cut into gently, weigh two components；Light component is directly as low-sulphur oil blend component, heavy constituent
It is then the diesel component for being enriched sulfide；The method of the present invention, can be greatly reduced the sulphur in gasoline
Content, while reducing the loss of octane number that sweetening process is brought.
The A of CN 102994148 provide a kind of method of deep desulfurization of gasoline, and gasoline stocks and hydrogen are mixed into
It is monoolefine to enter pre-hydrogenator by the diene hydrogenation in catalytic gasoline；Pre- hydrogenation products enter a water
Wash tower to be washed, the partial alkaline nitride in abjection gasoline, subsequently into a catalytic rectifying tower,
Vulcanize the part thiophene-based in gasoline in the presence of the alkene thiophene alkylation catalyst of catalytic rectifying tower top
Thing increases weight, while gasoline is cut into light petrol, heavy petrol, three components of light diesel fuel；Heavy gasoline components enter
Selectable hydrogenation reactor carries out deep desulfuration, after the hydrogen sulfide that desulfurization product is produced in elimination reaction with
Light petrol is mixed to get the gasoline products of deep desulfuration；The light diesel fuel of bottom of towe as hydrodesulfurization raw material, or
Make the mediation of low-coagulation diesel oil blend component to dispatch from the factory.
In sum, from terms of the retrieval of patent document, more full fraction hydrogenating gasoline is studied and applied at present
Desulfurization technology and weight gasoline selective hydrodesulfurizationmodification technology, in producing country's V normal benzines, gasoline depth
Degree desulfurization requirement equipment material is high, while there is alkene degree of saturation greatly, octane number loses big problem.
Therefore, further removing product in sulphur, reduce product loss of octane number be current technological development difficult point and
Focus.
The content of the invention
Present in prior art while catalytic gasoline deep desulfuration, the loss of octane number of gasoline is larger to ask
Topic, it is de- it is an object of the invention to provide a kind of gasoline deep of the transfer reaction of sulphur containing gasoline alkylate distillation technology
Sulphur group technology, gasoline alkylate sulphur transfer reaction distillation technology and Etherification of Light FCC Gasoline and heavy petrol hydrogenation are taken off
Sulphur is combined, the method with technological process flexibly, reduced investment, gasoline octane while deep desulfuration
Value loss is few, it is also possible to be combined with the existing gasoline desulfurization in refinery and raising octane number device.
The present invention provides a kind of deep gasoline desulfurization device adopting, wherein, including pre- hydrogasoline Cutting Tap, light vapour
Oily methyltertiarvbutyl ether reactor, catalytic rectifying column, heavy petrol hydrodesulphurisatioreactors reactors；
The pre- hydrogasoline Cutting Tap is provided with the outlet of tower top light petrol, the outlet of bottom of towe heavy petrol and full cut
Gasoline entrance；
The Etherification of Light FCC Gasoline reactor is provided with pre- etherified benzine entrance and the outlet of bottom of towe etherified benzine；
The catalytic rectifying column is provided with fuel dispensing outlet in tower top, the outlet of bottom of towe heavy naphtha and urges in advance
Change oil product of gasoline entrance；
The heavy petrol hydrodesulphurisatioreactors reactors are provided with tower top and are hydrogenated with sweet oil product entrance, and bottom of towe desulfurization in advance
Heavy petrol outlet afterwards；
After full distillation gasoline pipeline is connected with hydrogen gas lines, then with the full distillation gasoline entrance by pipe
Line is connected；After tower top light petrol outlet is connected by pipeline with toluene pipeline, then with the pre- ether
Change light petrol entrance to be connected by pipeline；The bottom of towe heavy petrol outlet enters with the pre- catalytic gasoline oil product
Mouth is connected by pipeline；The bottom of towe heavy naphtha outlet is connected by pipeline with the hydrogen gas lines
After, then be hydrogenated with sweet oil product entrance in advance with the tower top and be connected by pipeline.
The present invention also provides a kind of deep desulfurization of gasoline method, and the method is filled using above-mentioned deep desulfurization of gasoline
Put, comprise the following steps：
(1) after full distillation gasoline mixes with hydrogen, the pre- hydrogenation light petrol Cutting Tap is initially entered, is taken off
After diolefin and mercaptan, the cutting of weight component is completed, cut point is 60~70 DEG C, obtains tower top light petrol
With bottom of towe heavy petrol；
(2) tower top light petrol described in step (1) enters the Etherification of Light FCC Gasoline reactor, enters with methyl alcohol
Row etherification reaction, sulfur content is less than 10 μ g/g in the etherified benzine after etherification reaction, and octane number is improved
3~5 units；
(3) bottom of towe heavy petrol described in step (1) enters the catalytic rectifying column, and the catalysis is anti-
Answer rectifying column that gasoline alkylate sulfur transfer catalyst is housed, work of the thiophene-type sulfide in gasoline in catalyst
There is alkylated reaction with light olefin with lower, obtain middle gasoline, bottom of towe heavy naphtha after tower top desulfurization,
Middle gasoline and the bottom of towe heavy naphtha cut point are 110~120 DEG C after the tower top desulfurization；
(4) olefin(e) centent is down to 25% in bottom of towe heavy naphtha described in step (4), into described heavy
Gasoline hydrodesulfurizationmethod reactor, obtains heavy petrol after bottom of towe desulfurization.
Deep desulfurization of gasoline method of the present invention, wherein, catalytic reaction rectification described in step (3)
The process conditions of tower are preferably：Feed liquid weight space velocity is 0.5~1h-1, the operation temperature control of conversion zone
At 90~120 DEG C, bottom temperature is 130 DEG C~160 DEG C, 60~80 DEG C of reflux section temperature, and tower top temperature is not
More than 40 DEG C, reflux ratio is 1：2~2：1, catalytic rectifying column atmospheric operation.
Deep desulfurization of gasoline method of the present invention, wherein, thiophene-based vulcanization in middle gasoline after the desulfurization
The thing rate of transform is preferably greater than 90%, and middle sulfur content in gasoline is preferably below 15 μ g/g after the desulfurization, pungent
Alkane value is not lost.
Deep desulfurization of gasoline method of the present invention, wherein, heavy petrol adds described in the step (5)
The process conditions of hydrogen desulfurization reactor are：, preferably at 260~280 DEG C, volume space velocity is preferred during liquid for operation temperature
1.0~5.0h-1, hydrogen-oil ratio is preferably 100：1~500：1, operating pressure preferably 1.0~3.0MPa.
Deep desulfurization of gasoline method of the present invention, wherein, sulfur content is less than in heavy petrol after the desulfurization
It is preferred that 10 μ g/g, loss of octane number is preferably smaller than 2 units.
The present invention can also details are as follows：
The present invention is distributed according to the different hydrocarbons of catalytically cracked gasoline composition and sulphidic species, by light petrol ether
Change, middle gasoline alkylate sulphur is shifted and is integrated combining for heavy petrol hydrodesulfurization Process improvement, group
The group technology of high-quality state V normal benzine blend components is produced into deep desulfurization of gasoline.Its technological process
See accompanying drawing 1, full distillation gasoline A mixes the pre- hydrogenation light petrol for being introduced into Etherification of Light FCC Gasoline unit with hydrogen B
Cutting Tap 1, mercaptan sulfur and alkadienes in removing feed gasoline, feed gasoline is cut into two kinds of groups of weight
Point, weight component cut point is 60 DEG C~70 DEG C, and light petrol removes light petrol ether from after the extraction of hydrogenation distillation tower top
Change reactor 2 carries out etherification reaction with methyl alcohol C；Go to be filled with the anti-of catalyst more than 70 DEG C of gasoline components
Answer in rectifying column 3, the thiophene-type sulfide in gasoline occurs alkyl in the presence of catalyst with light olefin
Change sulphur transfer reaction, the thiophenic sulfur after alkylated reaction is transferred in heavy component, more than 70 DEG C of gasoline components
Reacted rectifying column cuts into two kinds of components of middle heavy petrol, and cut point is 110 DEG C~120 DEG C, gasoline in desulfurization
E is extracted out from tower top；The relatively low sulfur-rich heavy petrol of olefin(e) centent discharges heavy petrol hydrodesulfurization list from tower reactor
Unit, deep desulfuration is carried out into heavy petrol hydrodesulphurisatioreactors reactors 4, and the heavy petrol F after desulfurization is light with etherificate
Gasoline D and middle gasoline E are reconciled, can be as the blend component of production high-quality state V gasoline.
Its feature is described as follows step：
(1) the full distillation gasoline of gasoline initially enters Etherification of Light FCC Gasoline unit, and catalytically cracked gasoline cut enters
It is filled with after removing diolefin and mercaptan in the light petrol Cutting Tap of the de- diene removal of mercaptans of selective hydrogenation, weight
Component is cut, and cut point is 60~70 DEG C.
(2) light petrol in step (1) enters Etherification of Light FCC Gasoline unit, and etherification reaction is carried out with methyl alcohol,
Light petrol sulfur content is less than 10 μ g/g after etherification reaction, and octane number improves 3~5 units.
(3) entering equipped with gasoline alkylate sulphur transfer reaction more than 70 DEG C of gasoline fractions in step (1)
In catalyst distillation column reactor section.More than 70 DEG C of gasoline fractions middle heavy two kinds of vapour is cut into through catalytic rectifying tower
Oil distillate, to there is alkylation in the thiophene-type sulfide in middle gasoline anti-in the presence of catalyst with light olefin
Should.
(4) blend component of the middle gasoline in step (3) directly as clean gasoline.
(5) the heavy petrol olefin(e) centent in step (3) is reduced to 25% or so, de- into heavy petrol hydrogenation
Reaction of Salmon-Saxl device desulfurization.
(6) process conditions of catalytic rectifying tower operation are in the step (3)：Feed liquid weight space velocity
It is 0.5~1h-1, at 90 DEG C~120 DEG C, bottom temperature is 130 DEG C~160 for the operation temperature control of conversion zone
DEG C, reflux section temperature 60 C~80 DEG C, tower top temperature is not more than 40 DEG C, reflux ratio control 1：2~2：1,
Catalytic rectifying tower atmospheric operation.In, heavy petrol cut point be 110~120 DEG C, in middle gasoline thiophene-based vulcanization
The thing rate of transform be more than 90%, through alkyl sulfur transfer reaction after, middle content of sulfur in gasoline be below 15 μ g/g,
Octane number does not lose.
(7) heavy petrol hydrodesulfurization reaction process conditions in the step (5)：Operation temperature is at 260 DEG C
~280 DEG C, 1.0~5.0h of volume space velocity during liquid-1, hydrogen-oil ratio is 100：1~500：1, operating pressure
1.0~3.0MPa, the heavy petrol sulfur content after desulfurization is less than 10 μ g/g, and loss of octane number is less than 2 units.
(8) heavy petrol after desulfurization is reconciled with etherified benzine and middle gasoline, by the group technology,
Content of sulfur in gasoline is less than 10 μ g/g after mediation, and octane number increases 1-2 unit, can be as production high-quality
The blend component of state's V normal benzines.
It is combined by Etherification of Light FCC Gasoline, the transfer of middle gasoline alkylate sulphur and heavy petrol hydrodesulfurizationmodification modification technology
Group technology, the light petrol cut point of Etherification of Light FCC Gasoline unit is 60~70 DEG C, and the light petrol for cutting out enters
Etherification of Light FCC Gasoline unit, etherification reaction is carried out with methyl alcohol, and light petrol sulfur content is less than 10 μ g/g, and octane number is carried
3~5 units high；Catalytic distillation alkyl sulfur buanch unit, middle heavy petrol cut point is 110~120 DEG C,
In middle gasoline the thiophene-type sulfide rate of transform be more than 90%, through alkyl sulfur transfer reaction after, middle gasoline sulfur contains
It is below 15 μ g/g to measure, and octane number does not lose；After the hydrogenated desulfurization modification of heavy petrol, sulfur content is less than
10 μ g/g, loss of octane number is less than 2 units.
Gently, in, after heavy petrol mediation, the sulfur content of full distillation gasoline is less than 10 μ g/g, and octane number increases
1-2 unit, can be as the blend component of production high-quality state V gasoline.
The present invention has the following advantages：
The present invention first adds gasoline alkylate sulphur transfer reaction distillation technology and Etherification of Light FCC Gasoline and heavy petrol
Combining for hydrogen sulfur removal technology Process improvement is integrated, composition deep desulfurization of gasoline production high-quality state V marks
The group technology of quasi- gasoline blend component, flexibly, investment is simple, can be with the existing vapour in refinery for technological process
Oily desulfurization and raising octane number device are combined.Gasoline alkylate sulphur transfer reaction distillation technology and light petrol ether
Change and heavy petrol hydro-upgrading technology is combined, light petrol cut point can be reduced, obtain the etherificate without sulphur light
Gasoline；After middle gasoline is through catalytic distillation alkyl sulfur transfer reaction, without hydrodesulfurization, can be directly as
Blend component；Heavy petrol initial boiling point can bring up to 120 DEG C, the heavy petrol hydrodesulfurization unit of reduction it is negative
Lotus, due to the olefin(e) centent reduction in heavy petrol, while deep desulfurization of gasoline, it is possible to reduce gasoline is pungent
The loss of alkane value.
Brief description of the drawings
Fig. 1：Deep gasoline desulfurization device adopting figure
Wherein, reference
1 pre- hydrogenation light petrol Cutting Tap
2 Etherification of Light FCC Gasoline reactors
3 catalytic rectifying columns
4 heavy petrol hydrodesulphurisatioreactors reactors
5 full distillation gasoline entrances
Fuel dispensing outlet in 6 tower tops
7 bottom of towe heavy petrol are exported
8 pre- etherified benzine entrances
9 bottom of towe etherified benzines are exported
Fuel dispensing outlet in 10 tower tops
11 pre- catalytic gasoline oil product entrances
12 bottom of towe heavy naphthas are exported
13 tower tops are hydrogenated with sweet oil product entrance in advance
Heavy petrol outlet after 14 bottom of towe desulfurization
The full distillation gasolines of A
B hydrogen
C methyl alcohol
D etherified benzines
Middle gasoline after E desulfurization
Heavy petrol after F desulfurization.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is premised on technical solution of the present invention
Under implemented, give detailed implementation method and process, but protection scope of the present invention be not limited to it is following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
Referring to the drawings 1, the present embodiment be deep gasoline desulfurization device adopting figure, including pre- hydrogasoline Cutting Tap 1,
Etherification of Light FCC Gasoline reactor 2, catalytic rectifying column 3, heavy petrol hydrodesulphurisatioreactors reactors 4；
The pre- hydrogasoline Cutting Tap is provided with tower top light petrol outlet 6, bottom of towe heavy petrol outlet 7 and complete
Distillation gasoline entrance 5；
The Etherification of Light FCC Gasoline reactor 2 is provided with pre- etherified benzine entrance 8 and the outlet of bottom of towe etherified benzine
9；
The catalytic rectifying column 3 is provided with fuel dispensing outlet 10, bottom of towe heavy naphtha outlet 12 in tower top
And pre- catalytic gasoline oil product entrance 11；
The heavy petrol hydrodesulphurisatioreactors reactors 4 are provided with tower top and are hydrogenated with sweet oil product entrance 13, Yi Jita in advance
Heavy petrol outlet 14 after the desulfurization of bottom；
After full distillation gasoline A pipelines are connected with hydrogen B pipelines, then with the full distillation gasoline entrance
5 are connected by pipeline；After the tower top light petrol outlet 6 is connected by pipeline with toluene C pipelines,
It is connected by pipeline with the pre- etherified benzine entrance 8 again；Bottom of towe heavy petrol outlet 7 with it is described
Pre- catalytic gasoline oil product entrance 11 is connected by pipeline；The bottom of towe heavy naphtha outlet 12 is by pipe
After line is connected with the hydrogen B pipelines, then sweet oil product entrance 13 is hydrogenated with advance with the tower top passes through
Pipeline is connected.
The embodiment that the present invention is given is that the gasoline deep of the transfer reaction distillation technology of sulphur containing gasoline alkylate takes off
The group technology implementation result of sulphur, group technology is by Etherification of Light FCC Gasoline unit, gasoline alkylate sulphur buanch unit
And heavy petrol hydrodesulfurizationunit unit is combined, technological process is as described in Figure 1.
The raw material oil property of table 1
| Project | Unit | Full fraction |
| HK | ℃ | 34.7 |
| 10% recovered temperature | ℃ | 53.0 |
| 50% recovered temperature | ℃ | 95.0 |
| 90% recovered temperature | ℃ | 169.5 |
| KK | ℃ | 196.6 |
| Sulfur content | ug/g | 226 |
| RON | - | 90.3 |
The technological condition of Etherification of Light FCC Gasoline unit and heavy petrol hydrodesulfurizationunit unit is shown in Table in each embodiment
2, the technological condition of alkylation desulfurization of gasoline unit is shown in Table 3, is described in detail below.
Embodiment 1：
Etherification of Light FCC Gasoline reaction temperature is 60 DEG C in the embodiment, and reaction pressure is 0.4MPa；Gasoline alkyl
Change sulphur buanch unit process conditions：Feed weight air speed 0.5h-1, reflux ratio 2：1, reaction pressure normal pressure；
Heavy petrol hydrodesulfurization reaction temperature is 260 DEG C, hydrogen-oil ratio 500：1, volume space velocity 1.0h during liquid-1, instead
Answer pressure 1.0MPa.
Embodiment 2：
Etherification of Light FCC Gasoline reaction temperature is 65 DEG C in the embodiment, and reaction pressure is 0.4MPa；Gasoline alkyl
Change sulphur buanch unit process conditions：Feed weight air speed 0.5h-1, reflux ratio 1：1, reaction pressure normal pressure；
Heavy petrol hydrodesulfurization reaction temperature is 270 DEG C, hydrogen-oil ratio 300：1, volume space velocity 1.0h during liquid-1, instead
Answer pressure 2.0MPa.
Embodiment 3：
Etherification of Light FCC Gasoline reaction temperature is 70 DEG C in the embodiment, and reaction pressure is 0.4MPa；Gasoline alkyl
Change sulphur buanch unit process conditions：Feed weight air speed 0.5h-1, reflux ratio 1：2, reaction pressure normal pressure；
Heavy petrol hydrodesulfurization reaction temperature is 280 DEG C, hydrogen-oil ratio 100：1, volume space velocity 1.0h during liquid-1, instead
Answer pressure 3.0MPa.
Embodiment 4：
Etherification of Light FCC Gasoline reaction temperature is 60 DEG C in the embodiment, and reaction pressure is 0.4MPa；Gasoline alkyl
Change sulphur buanch unit process conditions：Feed weight air speed 1h-1, reflux ratio 2：1, reaction pressure normal pressure；Weight
Gasoline hydrodesulfurizationmethod reaction temperature is 260 DEG C, hydrogen-oil ratio 500：1, volume space velocity 2.0h during liquid-1, reaction
Pressure 1.0MPa.
Embodiment 5：
Etherification of Light FCC Gasoline reaction temperature is 65 DEG C in the embodiment, and reaction pressure is 0.4MPa；Gasoline alkyl
Change sulphur buanch unit process conditions：Feed weight air speed 1h-1, reflux ratio 1：1, reaction pressure normal pressure；Weight
Gasoline hydrodesulfurizationmethod reaction temperature is 270 DEG C, hydrogen-oil ratio 300：1, volume space velocity 2.0h during liquid-1, reaction
Pressure 2.0MPa.
Embodiment 6：
Etherification of Light FCC Gasoline reaction temperature is 70 DEG C in the embodiment, and reaction pressure is 0.4MPa；Gasoline alkyl
Change sulphur buanch unit process conditions：Feed weight air speed 1h-1, reflux ratio 1：2, reaction pressure normal pressure；Weight
Gasoline hydrodesulfurizationmethod reaction temperature is 280 DEG C, hydrogen-oil ratio 100：1, volume space velocity 2.0h during liquid-1, reaction
Pressure 3.0MPa.
The technological condition of the Etherification of Light FCC Gasoline unit of table 2 and heavy petrol hydrodesulfurizationunit unit
Each embodiment gasoline alkylate prevailing operating conditions of table 3
It is light in each embodiment, in, the heavy petrol and sulfur content and octane number situation of whole-distillate gasoline are shown in after reconciling
Table 4
Each gasoline component property of table 4
As can be seen from Table 4 using the process conditions of each embodiment, the sulfur content of the full distillation gasoline after mediation
Less than 10 μ g/g, octane number increased 1~1.9 unit, can be as production high-quality state V gasoline
Blend component.
Claims (6)
1. a kind of deep gasoline desulfurization device adopting, it is characterised in that including pre- hydrogasoline Cutting Tap, light vapour
Oily methyltertiarvbutyl ether reactor, catalytic rectifying column, heavy petrol hydrodesulphurisatioreactors reactors；
The pre- hydrogasoline Cutting Tap is provided with the outlet of tower top light petrol, the outlet of bottom of towe heavy petrol and full cut
Gasoline entrance；
The Etherification of Light FCC Gasoline reactor is provided with pre- etherified benzine entrance and the outlet of bottom of towe etherified benzine；
The catalytic rectifying column is provided with fuel dispensing outlet in tower top, the outlet of bottom of towe heavy naphtha and urges in advance
Change oil product of gasoline entrance；
The heavy petrol hydrodesulphurisatioreactors reactors are provided with tower top and are hydrogenated with sweet oil product entrance, and bottom of towe desulfurization in advance
Heavy petrol outlet afterwards；
After full distillation gasoline pipeline is connected with hydrogen gas lines, then with the full distillation gasoline entrance by pipe
Line is connected；After tower top light petrol outlet is connected by pipeline with toluene pipeline, then with the pre- ether
Change light petrol entrance to be connected by pipeline；The bottom of towe heavy petrol outlet enters with the pre- catalytic gasoline oil product
Mouth is connected by pipeline；The bottom of towe heavy naphtha outlet is connected by pipeline with the hydrogen gas lines
After, then be hydrogenated with sweet oil product entrance in advance with the tower top and be connected by pipeline.
2. a kind of deep desulfurization of gasoline method, deep desulfurization of gasoline dress described in the method usage right requirement 1
Put, comprise the following steps：
(1) after full distillation gasoline mixes with hydrogen, the pre- hydrogenation light petrol Cutting Tap is initially entered, is taken off
After diolefin and mercaptan, the cutting of weight component is completed, cut point is 60~70 DEG C, obtains tower top light petrol
With bottom of towe heavy petrol；
(2) tower top light petrol described in step (1) enters the Etherification of Light FCC Gasoline reactor, enters with methyl alcohol
Row etherification reaction, sulfur content is less than 10 μ g/g in the etherified benzine after etherification reaction, and octane number is improved
3~5 units；
(3) bottom of towe heavy petrol described in step (1) enters the catalytic rectifying column, and the catalysis is anti-
Answer rectifying column that gasoline alkylate sulfur transfer catalyst is housed, work of the thiophene-type sulfide in gasoline in catalyst
There is alkylated reaction with light olefin with lower, obtain middle gasoline, bottom of towe heavy naphtha after tower top desulfurization,
Middle gasoline and the bottom of towe heavy naphtha cut point are 110~120 DEG C after the tower top desulfurization；
(4) olefin(e) centent is down to 25% in bottom of towe heavy naphtha described in step (3), into described heavy
Gasoline hydrodesulfurizationmethod reactor, obtains heavy petrol after bottom of towe desulfurization.
3. deep desulfurization of gasoline method according to claim 2, it is characterised in that in step (3)
The process conditions of the catalytic rectifying column are：Feed liquid weight space velocity is 0.5~1h-1, conversion zone
At 90~120 DEG C, bottom temperature is 130 DEG C~160 DEG C, 60~80 DEG C of reflux section temperature for operation temperature control,
Tower top temperature is not more than 40 DEG C, and reflux ratio is 1：2~2：1, catalytic rectifying column atmospheric operation.
4. deep desulfurization of gasoline method according to claim 3, it is characterised in that after the desulfurization
The thiophene-type sulfide rate of transform is more than 90% in middle gasoline, and middle sulfur content in gasoline is 15 μ g/g after the desulfurization
Hereinafter, octane number does not lose.
5. the deep desulfurization of gasoline method according to any one of claim 2~4, it is characterised in that institute
The process conditions for stating heavy petrol hydrodesulphurisatioreactors reactors described in step (4) are：Operation temperature is 260~280
DEG C, 1.0~5.0h of volume space velocity during liquid-1, hydrogen-oil ratio is 100：1~500：1,1.0~3.0MPa of operating pressure.
6. deep desulfurization of gasoline method according to claim 5, it is characterised in that after the desulfurization
Sulfur content is less than 10 μ g/g in heavy petrol, and loss of octane number is less than 2 units.
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| CN111892948A (en) * | 2020-06-15 | 2020-11-06 | 新疆寰球工程公司 | Processing method for hydrogenation and octane number loss reduction of catalytically cracked gasoline |
| CN113122326A (en) * | 2020-01-15 | 2021-07-16 | 中国石油天然气股份有限公司 | Deep desulfurization method for full-fraction catalytic cracking gasoline |
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| CN105062559A (en) * | 2015-08-10 | 2015-11-18 | 华南理工大学 | Novel process for reducing energy consumption of catalytic gasoline hydrogenation refining process |
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| CN105062559A (en) * | 2015-08-10 | 2015-11-18 | 华南理工大学 | Novel process for reducing energy consumption of catalytic gasoline hydrogenation refining process |
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| CN113122326A (en) * | 2020-01-15 | 2021-07-16 | 中国石油天然气股份有限公司 | Deep desulfurization method for full-fraction catalytic cracking gasoline |
| CN113122326B (en) * | 2020-01-15 | 2023-04-07 | 中国石油天然气股份有限公司 | Deep desulfurization method for full-fraction catalytic cracking gasoline |
| CN111892948A (en) * | 2020-06-15 | 2020-11-06 | 新疆寰球工程公司 | Processing method for hydrogenation and octane number loss reduction of catalytically cracked gasoline |
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